Cellular phenolic resin products



States Patent Office 2,798,054 Patented July 2, 1957 CELLULAR PnENoLtoRESIN PaonUcrs N Drawing. Application April 9, 1952, Serial No. 281,464

Claims. (Cl. 260-25) This invention relates to cellular materials andrelates more particularly to cellular phenolic resinproducts and tothemethods of making the same.

Relatively low density cellular phenolic resin materials have beendeveloped and introduced but so far as we are aware these products havebeen brittle and possessed poor physical strength characteristics. Theseattributes have, of course, prevented any appreciable acceptance of. thematerials for commercial or industrial applications, particularly wherestrength is a requirement. It is an object of the present invention toprovide cellular phenolic resinproducts having good physical strengthcharacteristics and, therefore, well suited for many applications forwhich the earlier products. of this kind were inadequate. and unsuited.The cellular products of this invention are strong and tough and,therefore, are useful in structural applications, etc. where they arerequired to serve as load.

carriers and where they may be called upon to withstand impact.

It is another object of our invention to provide cellular phenolic resinproducts that have substantially uniform cell structures and that do notdevelopvoids or cracks fections made the products unsuitable for mostapplications. On the other hand the products of this invention are ofsubstantially uniform cellular structure and may be made in large bodiesor masses without the development of cracks or discontinuities.

A further object of the invention is to provide cellular plasticproducts of the kind described that are of low or relatively low densityand yet are strong and tough to be well suited for use in aircraft andinindustrial applications where relatively low weight coupled withsubstantial strength are important considerations.

Other objects and features of our invention will become apparent fromthe following specification or description.

In preparing the foamed or cellular plastic products we employ asuitable or selected phenol-aldehyde resol, a polyamide or protein or aformalized polyamide or protein, a gassing agent and an acid catalyst.Otheringredients such as polyvinyl alcohol may also be incorporated inthe formulations and blends or mixtures of selected phenol-aldehyderesols may be used.

The phenol-aldehyde resol or resols employed are primarily derived fromthe reaction of phenols and aldehydes and their various analogues.Reference is made to our copending application, Serial No. 231,673,filed June 14, 1951 which specifically describes a large number ofpehnol-aldehyde resols suitable for use in preparing the products of thepresent invention. We will herein describe several typical examples ofresols that are suitable for use in preparing the product or cellularmaterial of this inven tion although we do not wish to be limited tothese specific examples. The phenolic resins or phenol-aldehyde resolsare acid catalyzable and water miscible, have a specific gravity ofbetween 1.15 and 1.35 and a pH of about 7 and are the reaction productsof a phenolic compound, an aldehyde and an alkaline catalyst. Thefollowing are illustrative formulations of the phenolaldehyderesolssuitable for incorporation in the reactant mixtures for making thecellular plastic products of the invention:

RESIN 1 Phenol lmol. Formaldehyde l to 2.5 mols. Barium hydroxide 8H2O0.003 to 0.020 mol.

RESIN 2 Para-isopropyl phenol 1 mol. Formaldehyde 1 to 2.5 mols. Calciumcarbonate 0.003;to 0.020 mol.

RESIN 3 Phenol u} '1' mol total (the para- Parachloro phenol chlorophenol being in the proportion of from 5 to by mol weight).

Formaldehyde l to 2.5 mols.

Barium hydroxide 8H2O 0.003 to 0.020 mol,

RESIN 4 Phenol 1 mol.

gmglakllehyde 1 was mols total (the UT ura furfural being in theproportion of from 5 to 50% by mol weight).

Barium. hydroxide 8H2O 0.003 to 0.20 mol.

RESIN 5 Phenol 1 mol.

Methyl ethyl ketone 0.5 to 1 mol.

Formaldehyde l to 2.5 mols.

Barium hydroxide SHzO 0.003 to 0.020 mol.

RESIN 6 Phenol" 1 mol.

Formaldehyde 1 to 2.5 mols.

Polyvinyl alcohol l to 15% by weight of the total weight of the phenoland formaldehyde.

Barium hydroxide 8H2O 0.003 to 0.020 mol.

RESIN 7 Phenol lmol.

Furfural 1 to 2.5 mols total (the fur- Formaldehyde fural being in theproportion of from 5 to 50% by mol weight).

Polyvinyl alcohol 5 to 50 grams.

Barium hydroxide 8I-I2O 0.003 to 0.020 mol.

RESIN 8 Phenol Resorcinol 1 mol total (the rcsorcinol being in theproportion of from 5 to 75% by mol weight).

Formaldehyde 1 to 2.5 mols.

Barium hydroxide 8H2O 0.003 to 0.020 mol.

Polyvinyl alcohol l to 15 percent by weight of the combined weight ofthe other components.

The formaldehyde used in synthesizing the above phenol-aldehyde resolsis preferably employed as an aqueous solution having a formaldehydeconcentration of from 30 to 40% by weight and usually about 37% byweight. The phenol-aldehyde resols, such as above described, may be usedseparately or in selected blends or mixtures in preparing the reactantmixtures or formulations of the invention. The phenol-aldehyde resol, ora blend thereof, is used in the proportion of from about 68% to about90% by weight of the total reactant mixture.

The catalyst which We prefer to employ is a blend or mixture of acids inaqueous solution although other acid catalysts may be used if desired.The blended acid catalyst which has been found to be especiallyeffective in foaming the phenol-aldehyde resol and polyamide or proteinmixture comprises a sulfonic acid, or the equivalent, and a phosphoricacid such as, n-metaphosphoric acid, pyro phosphoric acid, hexametaphosphoric acid, trimeta phosphoric acid and dimeta phosphoric acid. Thephosphoric acid serves to control the cure rate ofthe foamed resinousmass. The sulfonic acids or sulfonic acid derivatives that may beemployed in this catalyst blend include benzene sulfonic acid, phenolsulfonic acid, metabenzene di-sulfonic acid, and toluene sulfonic acidThe catalyst may include, for example:

The benzene sulfonic acid, or the equivalent thereof, the phosphoricacid solution and the water of the catalyst may be employed in theproportion ranges of:

Catalyst a'bcde benzene sulfonic acid (or equivalent) percent 20 20 20 550 85% aqueous orthophosphoric acid do 45 70 75 25 water do 70 35 10 Theacid catalyst blend, together with the gassing agent, assures thecontrolled rise of the phenolic resin mass and assists in producing thedesirable physical strength characteristics of the resultant cellularproducts. The catalyst serves to liberate or generate hydrogen,nitrogen, carbon dioxide, or other gas to produce the foaming of theresin mass andalso acts to eifect a cure of the cellular or foamedresin. The concentration range of the catalyst mixture or blend ispreferably from 2.0 to 35 parts by Weight per 100 parts of the resin.

Other catalysts that may be used in the formulations of the invention inplace of the above described catalyst include aqueous solutions of:

p-Toluene sulfonic acid Benzene sulfonic acid Butyl sulfonic acidCamphor sulfonic acid Benzene m-disulfonic acid Beta-naphthalenesulfonic acid These may be employed in the proportion range of thepreviously described catalyst.

The gassing agent or agents used in preparing the cellularphenolicproducts may be metals such as aluminum, zinc, iron or magnesium individed form or a water-soluble substance that will evolve gas while incontact with the water soluble sulfonic acid. Aluminum, zinc, iron ormagnesium, preferably in atomized form of from 600 to 200 mesh, employedindividually or in suitable mixtures, are effective as gassing agents asare these metals in the form of leafing powders of the same orcomparable mesh. Sodium bicarbonate, potassium bicanbonate, lithiumbicarbonate, sodium carbonate, potassium carbonate, lithium carbonate,ammonium carbonate, sodium nitrite, potassium nitrite, etc. may be usedas the gassing agent in place of the divided metal or metals justmentioned. It is usually preferred to employ the desired divided metalor metals as they have been found to produce superior results. Thegassing agent is used in the proportion of from .05 to 5.0% by weight ofthe total mixture.

We have discovered that the use or inclusion of synthetic polyamides ornatural proteins in the reactant phenol-aldehyde resol foaming mixtureresults in or produces a cellular plastic product that is tough and thatpossesses superior physical strength characteristics. The polyamide orprotein thus employed is soluble in and copolymerizable with thephenolic resol, the preferred method of incorporation being by rapidagitation in the hot resol, preferably at less than 200 F., the resinadditives being finely divided. The polyamide or protein may beformalized either by the reaction of the same with the formaldehydecontained in the phenol-aldehyde resol or by treating or reacting thepolyamide or protein with aqueous formaldehyde, formaldehyde vapor or apolymerized formaldehyde such as trioxymethylene or para-formaldehydeprior to blending or mixing it with the phenol-aldehyde resol. Whereformaldehyde is used to pre-treat the polyamide or protein, it ispreferably in the form of an aqueous solution of from to 36%concentration by weight. In preformalizing the proteins or polyamidesfrom 0.01 to 5% of the formaldehyde is used with from 99.99% to 95% byweight of the protein or polyamide, the preferred proportion being about2% by weight of the formaldehyde solution to 98% by Weight of theselected protein or polyamide. The pre-treatment or pre-forrnalizing ofthe proteins has been found to improve the viscosity of the mixture andto assist in producing a tougher, stronger cellular plastic product. Thepolyamides or proteins or the pre-formalized polyamides or proteins maybe used singly or in combinations or blends to modify the phenolaldehyderesol with a total range of proportions of from 2 to 20% of the totalmixture. The proteins that may be used individually or in blends ormixtures in preparing the products of the invention include:

Casein Dried blood Gelatine Hide glue Dried milk Zein Egg albuminGliadin Hordein Keratin Lactalbumin Soyabean protein Peanut protein Thepolyamides used in the present fomulations for preparing the cellularphenolic products are the reaction products of certain dibasic acidswith diamines. The reaction of adipic acid with hexamethylene diamine istypical, producing a polyamide of the characteristic structure;

Polyamide 1 O(OHz)O-NH(CH2)FNH l i N where x=4 and 3 :6 for thehexamethylene adipamide unit. Other acids that are useful in thepreparation of the polyamides include malonic, succinic, glutaric,pimelic, suberic, sebacic, and azelaic. Other polyamides useful insynthesizing the polyamides are propylene diamine, 1,3 diamino butane,trimethylene diamine, tetramethylene diamine, pentamethylene diamine,decamethylene diamine, etc; di-secondary hexamethylene diamines such as(N,N diisobutyl hexamethylene diamine); and secondary-primary diaminessuch as n-monoisobutyl hexamethylene diamine. The polyamides suitablefor in-. corporation in the formulations and reaction products of thepresent invention include those described; in the W; H. Carothers PatentNumber 2,130,523, September 20, 1938, and the fusibility and solubility(necessary attributes of the polyamides employed in the presentinvention) of the polyamides are obtained and controlled by selectingthe reacting components so that the sumof the radical lengths exceedseight, the radical length in each case being the number of atoms in thechain of the radical. The polyamides have recurring structural units ofunit length exceeding eight, with the nitrogens in the polyamideattached to aliphatic carbon atoms' Thus the radical length of thehexamethylene adipamide unit is 14 and is determined as follows:

H O O 1 2 3 4 5 6 7 8 10 ll 12 13 14 The following are illustrative ofother polyamides-that may be employed in preparing the reaction productsof Polyamide The reaction product of hexadecamethylene dicarbox-.

ylic acid and pentamethylene diamine.

Polyamide 6 The reaction product of sebacic acid and decamethylenediamine.

In each of the polyamide examples given the reactants (the dibasic acidsand diamines) are used in chemically equivalent amounts.

The following. are illustrative examples of formulations for preparingor making the cellular phenolic resin products of the invention, theingredients being given in percentages by weight:

EXAMPLE 1 Percent Phenol-aldehyde resin No. 1 85 Polyamide No. l 5Catalyst 9.7 Aluminum powder 0.3

In this example the proportion of the resin or resol may be from 70 to88% with the polyamide in the proportion of from 2 to 20%.

EXAMPLE 2 Percent Phenol-aldehyde resin No. l 80 Polyamide No. 4 5Polyvinyl alcohol 5 Catalyst 9.7 Aluminum powder, 422 mesh 0.3

In Example 2 the resol may be employed in the proportion of from 68 to86%; the polyvinyl alcohol may be used in the proportion of from 2 toEXAMPLE 3 Percent Phenol-aldehyde resin No. l 70 Phenol-aldehyde resinNo. 7 5 Polyamide No. 3 10 Polyvinyl alcohol 5 Catalyst 9 Zinc powder,300 mesh.. 1

6 In Example 3, the phenol-aldehyde resin No. 1 may be used in theproportion of from 66% to 84% with the phenol aldehyde No. 7 used in theproportion of from 2 to 5%.

In this example the proportion of phenolic resin No. 1 may range from70% to 88% with the amount of protein glue ranging from 2% to 20%.

EXAMPLE 5 Percent Phenol-aldehyde resin No. 1--- 85 Protein (dried milk)5 Catalyst 9.7 Aluminum powder, 400 mesh 0.3

In Example 5 the phenol-aldehyde resin may be used in the amount of from70% to 88% with the protein varying in amount from 2% to 20%.

EXAMPLE 6 I Percent Phenol-aldehyde resin No. 1 85 Protein (dried blood)5 Catalyst 8.5 Iron Powder, 400mesh 1.5

In- Example 6 the resin may be employed in the proportion of from 70%to,88% and the protein may be used in the proportionof from 2 to 20% Ineach of the examples the polyamide or protein may, if desired, be usedin the proportion of from 2% to 20%.

If desired. or found more practical, the previously desoribedpre-formalized proteins may replace the polyamides in Examples 2 and 3.In the following Examples 7, 8 and 9, the pre-formalized polyamides arespecified, it being understood that other and equivalent polyamidestreated or reacted with formaldehyde or its homologues, may be employedinstead of those specified with the protein reacted with from 0.01% to5% by weight of formaldehyde or its homologue with 2% by weight of theIn Example 7-the resin may be used in the proportion of from 70% to 88%and the polyamide in the proportion of from 2 to 20%.

EXAMPLE 8 Percent Phenol-aldehyde resin No. 2 85 Formalized casein 5Catalyst V 9.7 Aluminum powder, 400 mesh 0.3

In this example the resin may be used in the proportion of from 70% to88% andthe pre-formalized casein in the proportion of from 2 to 20%EXAMPLE 9 Percent Phenol-aldehyde resin No. 1 88 Formalized zein protein2 Catalyst 9.5 Aluminum powder, 400 mesh 0.5 In this case the resin maybe employed in the proportion of from70% fto 88%v and thetire-formalized zein in the proportion of from 2.to 20%. p v In theabove examples the catalyst is preferably. the benzene sulfonicacid-orthophosphoric acid-water catalyst previously described, althoughthe other catalysts enumerated above may be used in place thereof. Wherepolyvinyl alcohol is included in the above examples it is usedtomodify'the phenol-aldehyde resol and may be replaced -by polyvinylalcohol chloride or by a combina tion of polyvinyl alcohol and polyvinylalcohol chloride to the extent specified in the examples.

In preparing thecellular phenolic resin products of the invention theselected resol(s) are first heat-blended with the protein or polyamide,and upon cooling, the other components with the exception'of'thecatalyst are incorporated and thoroughly mixed together to form a onepackage"mixture.' The catalyst constitutes the other componentor"packa'ge;"When'it' is desired to prepare and "apply orpourthe'foamed' productf'the' packages or componentsjust describedareth'oroughly mixed together and the resultant reactant mixtureis thenapplied by pouring, brushing, blading, dipping, or the like." Themixture foams and reacts at atmosphe'ricipress'ure and room temperaturesto produce the cellular product, the reaction being accompanied byexothermic heat which sets the foam or cellular mass. The product may bepost cured for several hours at a slightly elevated temperature, say atatemperature of from 150 F to 250 F.

- It'should be understood that the invention. is not to be based upon ordependent upon the theories which we have expressed. Nor is theinvention to be regarded as limited to the express procedure or materialset forth, these details being given'only by way of illustration and toaid in clarifying the invention. We do not regard such specific detailsas essential to the invention except insofar as they are expressed byway of limitation in the following claims in which it is our intentionto claim all novelty inherent in the invention as broadly as ispermissible in view of the prior art.

We claim:

1. The cellular plastic material which is the product of reaction of afoaming composition comprising, on an approximate percentage by weightbasis; from 68% to 90% of an acid catalyzable water misciblephenol-aldehyde resol, an aqueous blend of from 5 to 50% benzenesulfonic acid, from to 75% of an 85% concentration of orthophosphoricacid in an aqueous solution and from 10 to 70% water, said blend beingin the proportion of name to 35 parts by weight for each 100 parts byweight of the resol, from 0.05 to 5% of a gassing agent selected fromthe class consisting of finely divided aluminum, finely divided iron,finely divided zinc and finely divided magnesium, and from 2% to 20% ofthe reaction product of chemically equivalent amounts of glutaric acidand decamethylene diamine.

2. The cellular plastic material which is the product of reaction of afoaming composition comprising, on an approximate percentage by weightbasis; from 68% to 90% of an acid catalyzable water misciblephenol-aldehyde resol, an aqueous blend of from 5 to 50% benzenesulfonic a cid, from 10 to 75% of an 85% concentration oforthophosphoric acid in an aqueous solution and from 10 to 70% water,said blend being in the proportion of from 2 to 35 parts by weight foreach 100 parts by Weight of the resol, from 0.05% to 5% of a gassingagent selected from the class consisting of finely divided aluminum,finely divided iron, finely divided Zinc and finely divided magnesium,and from 2% to 20% of the reaction product of chemically equivalentamounts of dodecamethylene dicarboxylic acid and penta methylenediamine.

3. A' cellular plastic material which is the product of reaction of afoaming flowable composition comprising on a percentage by weightbasisfrom about 68% to 90% of an acid catalyzable water misciblephenol-aldehyde resol, from 2% to 20% of a synthetic linearpolycarbonamide predissolved in the resol the polycarbonamide beingprepared from chemically equivalent amounts of a dibasic acid and adiamine, the dibasic acid being selected from the group consisting ofadipic, malonic, succinic, glutaric, pimelic, suberic, sebacic andazelaic acids, and the diamine being selected from-the group consistingof hexamethylenediamine, propylene diamine, 1,3' diamino butane,trimethylene diamine, tetramethylcne diamine,

pentamethylene diamine, decamethylene diamine, N,N diisobutylhexamethylene diamine and n-monoisobutyl hexamethylene diamine,- from 2to 35 parts by weight per 100 parts by weight of the resol of an aqueousblend of sulfonic and orthophosphoric acids containing from 10 to water,and from 0.05% to 5% of finely divided metal selected from the classconsisting of aluminum, iron, zinc and magnesium.

4. A cellular plastic-material which is the product of reaction of afoaming flowable composition comprising on a percentage by weight basisfrom about 68% to 90% of an acid catalyzable water misciblephenol-aldehyde resol, from 2% to 20% of a synthetic polycarbonamideprepared from chemically equivalent amounts of a dibasic acid and adiamine, the dibasic acid being selected from the group consisting ofadipic, malonic, 'succin-ic, glutaric,; pimelic, suberic, sebacic'andazelaic acids, and the diamine being selected from the group consistingof hexamethylene diamine, propylene diamine, 1,3 diamino butane,trimethylene diamine, tetr amethyl'ene diamine, pentamethylene diamine,decamethylene diamine, N,N diisobutyl hexamethylene diamine andn-monoisobutyl hexamethylene diamine, from 2 to 35 parts by weight per100 parts by weight of the resol of an aqueous blend of sulfonic acidand orthophosphoric acid, from 0.05 to 5% of a finely divided metalselected from the class consisting of aluminum, iron, zinc andmagnesium.

5. The cellular plastic material which is the product of reaction of afoaming composition comprising, on an approximate percentage by weightbasis; from 68% to 90% of an acid catalyzable water misciblephenol-aldehyde resol, from 2% to 20% of a synthetic linearpolycarbonamide predissolved in the resol and being prepared fromchemically equivalent amounts of a dibasic acid and a diamine, thedibasic acid being selected from the group consisting of adipic,malonic, succinic, glut-aric, pimelic, suberic, sebacic and azelaicacids, and the diamine being selected from the group consisting ofhexamethylene diamine, propylene diamine, 1,3 diamino butane,trimethylene diamine, tetramethylene diamine, pentamethylene diamine,decamethylene diamine, N,N diisobutyl hexamethylenediamine andn-monoisobutyl hexamethylene diamine,'the nitrogens in the polyamidebeing attached to aliphatic carbon atoms, an aqueous blend of from 5 to50% benzene sulfonic acid, from 10 to of an concentration oforthophosphori acid in an aqueous solution and from 10 to 70% water,said blend being in the proportion of from 2 to 35 parts by weight foreach 100 parts by weight of the resol, and from 0.05% to 5% of a gassingagent selected from the class consisting of finely divided aluminum,finely divided iron, finely divided zinc and finely divided magnesium.

6. The cellular plastic material which is the product of reaction of afoaming composition comprising, on an approximate percentage by weightbasis; from 68% to of an acid catalyzable water miscible phenol-aldehyderesol, from 2% to, 20% of the reaction product of chemically equivalentamounts of adipic acid and hexamethylene diamine, said reaction productbeing predissolved in the resol, an aqueous blend of from 5 to 50%benzene sulfonic acid, from 10 to 75 of an 85% concentration oforthophosphoric acid in an aqueous solution and from 10 to 70% water,said blend being in the proportion of from 2 to 35 parts by weight foreach parts by weight of the resol, from 0.05 to 5% of a gassing agentselected from the class consisting of finely divided aluminum, finelydivided iron, finely divided zinc and finely divided magnesium.

7. The cellular plastic material which is the product of reaction of afoaming composition comprising, on an approximate percentage by weightbasis 85 of an acid catalyzable water miscible phenol-aldehyde resol, ofthe reaction product of chemically equivalent amounts of adipic acid andhexamethylene diamine, said reaction product being predissolved in theresol, 9.7% of an aqueous blend of benzene sulfonic acid andorthophosphoric acid, and from 0.05 to 5% of aluminum powder.

8. The cellular plastic material which is the product of reaction of afoaming composition comprising on a percent-age by weight basis; fromabout 68 to about 90% of an acid catalyzable water misciblephenol-aldehyde resol, about 5% of a synthetic linear polycarbonamidepredissolved in the resol, the polycarbonamide being prepared fromchemically equivalent amounts of a dibasic acid and a diamine, thedibasic acid being selected from the group consisting of adipic,malonic, succinic, glutaric, pimelic, suberic, sebacic and azelaicacids, and the diamine beng selected from the group consisting ofhexamethylene diamine, propylene diamine, 1,3 diamino butane,trimethylene diamine, tetramethylene diamine, pentamethylene diamine,decamethylene diamine, N,N diisobutyl hexamethylene diamine andn-monoisobutyl hexamethylene diamine, from 2 to 35 parts by weight per100 parts by weight of the resol of a catalyst comprising from to 70%water, from 10 to 75% of an 85% aqueous acid solution prepared from aphosphoric acid; pyro phosphoric acid; hexameta phosphoric acid; trimetaphosphoric acid and dimeta phosphoric acid and from 5 to 50% of asulfonic acid selected from the group consisting of benzene sulfonicacid; phenol sulfonic acid; meta benzene di-sulfonic and toluenesulfonic acid, and from 0.05 to 5% of a finely divided metal selectedfrom the class consisting of aluminum; iron; zinc; and magnesium.

9. The cellular plastic material which is the product of reaction of afoaming composition comprising on a percentage by weight basis; fromabout 68 to about 90% of an acid catalyzable water misciblephenolaldehyde resol, from 2 to 20% of a synthetic linearpolycarbonamide predissolved in the resol, the polycarbonamide beingprepared from chemically equivalent amounts of a dibasic acid and adiamine, the dibasic acid being selected from the group consisting ofadipic, malom'c, succinic, glutaric, pimelic, suberic, sebaci-c andazelaic acids, and the diamine being selected from the group consistingof hexamethylene diamine, propylene diamine, 1,3 diamino butane,tn'methylene diamine, tetramethylene diamine, pentamethylene diamine,decamethylene diamine, N,N diisobutyl hexamethylene diamine andn-monoisobutyl hexamethylene diamine, from 2 to 35 parts by weight per100 parts by weight of the resol of a catalyst comprising from 10 toWater, from 10 to of an aqueous acid solution prepared from a phosphoricacid selected from the group consisting of orthophosphoric acid; 11 metaphosphoric acid; pyro phosphoric acid; hexameta phosphoric acid; trimetaphosphoric acid and dimeta phosphoric acid and from 5 to 50% of asulfonic acid selected from the group consisting of benzene sulfonicacid; phenol sulfonic acid; meta benzene di-sulfonic and toluenesulfonic acid, and from 0.05 to 5% of a finely divided metal selectedfrom the class consisting of aluminum; iron; zinc; and magnesium.

10. The cellular plastic material which is the product of reaction of afoaming composition comprising on a percentage by weight basis; fromabout 68 to about of an acid catalyzable water miscible phenol-aldehyderesol, from 2 to 20% of a synthetic linear polycarbonamide predissolvedin the resol, the polycarbonamide being selected from the class Whosemembers consist of the reaction products of substantially chemicallyequivalent amounts of: azelaic acid and tetra methylene diamine,glutaric acid and decomethylene diamine, dodecamethylene dicarboxylicacid and pentamethylene diamine, hexadecomethylene dicarboxylic acid andpentamethylene diamine, sebacic acid and decamethylene diamine, andadipic acid and hexamethylene diamine, from 2 to 35 parts by weight perparts by weight of the resol of a catalyst comprising from 10 to 70%water, from 10 to 75% of an 85% aqueous acid solution prepared from aphosphoric acid selected from the group consisting of orthophosphoricacid; 11 meta phosphoric acid; pyro phosphoric acid; hexamet-aphosphoric acid; trimeta phosphoric acidand dimeta phosphoric acid andfrom 5 to 50% of a sulfonic acid selected from the group consisting ofbenzene sulfonic acid; phenol sulfonic acid; meta benzene di-sulfonicand toluene sulfonic acid, and from 0.05 to 5% of a finely divided metalselected from the class consisting of aluminum; iron; zinc; andmagnesium.

References Cited in the file of this patent UNITED STATES PATENTS2,323,831 Menger et al. July 6, 1943 2,328,398 Roskosky Aug. 31, 19432,373,401 King Apr. 10, 1945 2,394,993 Gardner Feb. 19, 1946 2,446,429Nelson Aug. 3, 1948 2,471,230 McKeever May 24, 1949 2,561,999 Stuck July24, 1951 2,582,228 Brinkema Jan. 15, 1952 2,608,536 Sterling Aug. 26,1952 2,683,697 Newell et a1. July 13, 1954

3. A CELLULAR PLASTIC MATERIAL WHICH IS THE PRODUCT OF REACTION OF AFOAMING FLOWABLE COMPOSITION COMPRISING ON A PERCENTAGE BY WEIGHT BASISFROM ABOUT 68% TO 90% OF AN ACID CATALYZABLE WATER MISCIBLEPHENOL-ALDEHYDE RESOL, FROM 2% TO 20% OF A SYNTHETIC LINEARPOLYCARBINAMIDE PREDISSOLVED IN THE RESOL THE POLYCARBONAMIDE DIBASICACID AND DIAMINE, THE DIBASIC ACID BEING SELECTED FROM THE GROUPCONSISTING OF ADIPIC, MALONIC, SUCCINIC, GLUTARIC, PIMELIC, SUBERIC,SEBACIC AND AZELAIC ACIDS, AND THE DIAMINE BEING SELECTED FROM THE GROUPCONSISTING OF HEXAMETHYLENE DIAMINE, PROPYLENE DIAMINE, 1,3 DIAMOBUTANE, TRIMETHYLENE DIAMINE, TETRAMETHYLENE DIAMINE PENTAMETHYLENEDIAMINE, DECAMETHYLENE DIAMINE,N,N DIISOBUTYL HEXAMETHYLENE DIAMINE ANDN-MONOISOBUTYL HEXAMETHYLENE DIAMINE, FROM 2 TO 35 PARTS BY WEIGHT PER100 PARTS BY WEIGHT OF THE RESOL OF AN AQUEOUS BLEND OF SULFONIC ANDORTHOPHOSPHORIC ACIDS CONTAINING FROM 10 TO 70% WATER, AND FROM 0.05% TO5% OF FINELY DIVIDED METAL SELECTED FROM THE CLASS CONSISTING OFALUMINUM, IRON, ZINC AND MAGNESIUM.